Pigment dyestuffs of the anthraquinone series



PIGMENT DYESTUFFS OF THE ANTHRA- QUINONE SERIES Wolfgang Schoenaner, Riehen, Switzerland, assignor to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application November 13, 1956 Serial No. 621,548

Claims priority, application Switzerland November 18, 1955 7"Claims. (Cl. 26 -368) The present invention relates to new valuable pigment dyestuifs of the anthraquinone series which correspond to the general formula In this formula:

NH: HzN O Each of x and x stands for hydrogen, fluorine, chlorine or bromine,

Each of y and y stands for hydrogen, fluorine, chlorine or bromine,

Each of R and R stands for hydrogen, chlorine, bromine, an alkoxy radical containing 1 to 3 carbon atoms, a mononuclear aryloxy, or a mononuclear arylsulfonyl V radical which may bear non-ionic substituents, and

R stands for the single carbon linkage, the bivalent radical of a saturated or unsaturated lower aliphatic hydrocarbon or the bivalent radical of a mononuclear or of a binuclear aromatic hydrocarbon.

The said radicals may contain non-ionic substituents and, in the case of the binuclear aromatic radicals, the nuclei are combined with each other either directly or through bridge members.

These new pigment dyestuffs of the anthraquinone series are obtained when 2 mols of a 1.4-diaminoanthraquinone of the general formula I N H2 A N Hi n wherein:

fluorine, chlorine or bromine,

fluorine, chlorine or bromine, and

R stands for hydrogen, chlorine, bromine,'an alkoxy radical containing 1 to 3 carbon atoms, or an aryloxy or arylsulfonyl radical, which may bear non-ionic substituents,

x-stands for hydrogen, y stands for hydrogen,

Of special interest are pigment dyestuffs corresponding to the Formula I, wherein Each of x, x, y and y stands for hydrogen or chlorine, Each of R and R stands for bromine or methoxy, and R stands for the single carbon linkage, the bivalent methylene radical, a bivalent tetramethylene radicalor a bivalent phenylene radical.

The most valuable pigment dyestufis however are those which correspond to the formula (I? NHQ Br (i N HO C-Rs-C O-IHN A (III) wherein R stands for the single carbon linkage, the bivalent methylene radical, a bivalent tetramethylene radical or a bivalent phenylene radical.

According to the process described above mixtures of pigment dyestufis of the anthraquinone series are obtained when two l.4-diaminoanthraquinones of the same general Formula II but diflerent from each other are condensed with the dicarboxylic acid halides defined above. These mixtures are very useful for obtaining any desired shade in the range of bordeaux to violet.

The following l.4-diaminoanthraquinones are enumerated as examples of those suitable for the formation of the new pigment dyestuffs of the anthraquinone series: 1.4 diaminoanthraquinone, 1.4-diamino-2-chloroanthraquinone, 1.4-diamino-2-bromanthraquinone and the 1.4- diaminoanthraquiuones of the general formulae HzN O A N H: (IV and 3 NH, (v)

wherein:

R stands for an'alkyl radical containing 1 to 3 carbon atoms or a phenyl radical, and

R for a phenyl, a methylphenyl or a chlorophenyl radical.

Water-solubilizing substituents, e. g. sulfonic acid, carboxylic acid and hydroxy groups, are outside the scope of this definition.

Examples of dicarboxylic acid halides which may be considered for the present purpose are oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, bromosuccinic acid dichloride, glutaric acid dichloride, methylglutaric acid dichloride, adipic acid dichloride, di-

' chloroadipic acid dichloride, methyladipic acid dichloride,

sebacic acid dichloride, fumaric acid dichloride, muconic acid dichloride, isophthalic acid dichloride, chloroisophthalic acid dichloride, terephthalic acid dichloride, chlo roterephthalic acid dichloride, 1.1-azobenzene-4.4-dicarboxylic acid chloride, 1.l-diphenyl-3.3'-dicarboxylic acid chloride, 1.l'-diphenyl-4.4'-dicarboxylic acid chloride, 1.1'diphenylmethane-4.4'-dicarboxylic acid chloride.

The acylation of the l;4-diarninoanthraquinones conforming to the present definition is accomplished by exposing them to the action of dicarboxylic acid chlorides in stoichiometric ratio, The dicarboxylic acid halides may be added to the solutionor suspensions as such or, more advantageously, in the form of solutions in organic solvents. Alternatively, they may be produced in the reaction mass from the corresponding dicarboxylic acids by reaction, for example with thionyl chloride. Acylation is conducted preferably in an organic medium, if desired in presence of an acid-binding agent such as pyridine or dimethylaminobenzene, and at temperatures ranging from 50 to 180 C. It is advisable to eliminate the hydrogen halide liberated in the course of the reaction from the condensation mass, e. g. by directing air or an inert gas over the surface. The dicarboxylic acid anthraquinonylamides thus formed are usually precipitated from the condensation mass while it is still hot; they are filtered off at'60100 C., washed with an alcohol and again with hot'water, and then dried. They can be brought into a suitable state of division for further processing as pigment dyestuifs by precipitation from concentrated sulfuric acid or by grinding.

The pigment dyestuffs are best converted into commercial paste form in suitable equipment such as roller mills, ball mills or homogenizers, if desired with the addition of dispersing agents, e. g. condensation products of naphthalene sulfonic acids and formaldehyde. The processed pigment dyestuffs may also be obtained in powder form by subjecting the pastes to a suitable drying process, for example drying, and re'grinding the dry powder in a suitable mill if desired.

The new pigment dyestufis of the anthraquinone series are employed for dyeing paper pulp and man-made fibers in the spinning mass, for printing textiles and paper, and for pigmenting synthetic resins, molded plastics, lacquers, emulsion paints, etc. They are characterized by their outstanding light fastness in these materials, and have the advantage over monocarboxylic acid anthraquinonylamides of being insoluble in organic solvents.

The following examples illustrate the invention but do not circumscribe its possible scope. All parts and percentages specified therein are by weight; the temperatures are given in degrees centigrade.

EXAMPLE I 23.8 parts of 1.4-diaminoanthraquinone in 660 parts of dry 1.2-dichlorobenzene are heated to 110. To the resulting solution at the-same temperature are added parts of dry pyridine, followed by a solution of 10.15 parts of benzene-1.3-dicarboxylic acid chloride in 29 parts of dry 1.2-dichlorobenzene, this being added dropwise in the course of 1% to 2 hours. The mass is stirred for 1 hour at 110, after which time the temperature is raised slowly to 135-140. As soon as the starting material is no longer indicated, the reaction mass is allowed to cool. The precipitated condensation product is then filtered off, washed successively with 1.2-dichlorobenzene, hot alcohol, and water, and finally dried.

parts of the product thus obtained are added to a five to ten times greater quantity of 97-100% sulfuric acid or 1-3% oleum. The suspension, at 0- 5", is stirred until the contents are dissolved, and the solution is then poured in a fine jet into 2000-3000 parts of ice water with vigorous stirring. The temperature of precipitation should notexceed The precipitated pigment dyestufi is filtered off, washed in neutral water, and if desired is treated with a dilute aqueous solution of sodium hydroxide or sodium carbonate to completely remove the adherent sulfuric acid. Following this 'it is again suction-filtered and washed in neutral water. The dried pigment dyestufi is a powder which dissolves in sulfuric 7 acid with a red coloration.

inorder to convert the pigment dyestuif into a commerclally usable form the filter cake, after neutral washing, is compounded with the sodium salt of dinaphthylmethane disulfonic acid in suitableapparatus-such as a roller mill, ball mill or homogenizer until the desired particle size is obtained. In this form the pigment dyestufi is ready for immediateuse in textile printing, thedyeing of paper pulp in the beater and of viscose rayon in the spinning solution. In these applications it yields bright violet shades with good fastness properties. The paste may also be worked up to a pigment powderin suitable drying equipment such as a spray drier.

A paste composed of parts of a 20% aqueous paste of the pigment dyestuff obtained according tothe above example, 400 parts of'tragac-anth 3%, 400 parts of a 50% aqueous solution of egg albumin and 100parts of a nonionic wetting agent are printed on a fabric of textile fiber. The print is dried and .then steamed for 30 minutes at 100-101.

In place of tragacanth and'egg albumin the printing paste maybe prepared with binders of the type used for fixing pigments to the fiber, for example those based on synthetic resins.

EXAMPLE 2 When the benzene-1.3-dicarboxylic acid chloride in Example 1 is replaced by benzene-1.4-dicarboxylic acid chloride, a pigment dyestufi is obtained which dyes viscose rayon in red-violet shades.

EXAMPLE 3 31.7 parts of l.4-diaminoQ-bromoanthraquinone in 660 parts of chlorobenzene are heated to the boil. The solution is dehydrated by distilling off 50 parts of a chlorobenzene-water mixture and is then drop-fed in the course of 1 to 1% hours with a solution of 7.65 parts of fumaric acid dichloride in 28 parts of chlorobenzene. The reaction mass is stirred for 1 hour at -120 and after this time is heated for-1 hour at It is then allowed to cool to 80, whereupon the condensation product is filtered ofi and washed, first with warm chlorobenzene, then with hot alcohol and finally with hot water, and subsequently dried.

The pigment dyestutf, of which a very good yield is obtained, dissolves in sulfuric acid with a red coloration. It can be converted into a pigment dyestuti preparation of suitable particle size by grinding in :a ball mill 'in the presence of water and a dispersing agent, e. .g. the condensation product of naphthalene sulfonic acid and formaldehyde. This preparation dyes viscose in the spinning solution in bordeaux shades.

A paper dyeing of mediumidepth can be produced :in the beater by mixing 2 parts of a 10% aqueous paste of the pigment dyestutf of this example into a pulp of 100 parts of bleached sulfite cellulose and 2000 parts of water. Vegetable sizing and simultaneous fixation of the pigment dyestufi on the paper fiber are effected by the successive addition of 40 parts of a 2.5% gum rosin size and 40 parts of a 5% solution of aluminum sulfate.

EXAMPLE 4 When 6.4 parts of oxalic acid dichloride are employed in place of the fumaric acid dichloride specified in Example 3 a condensation product is obtained which dissolves in sulfuric acid with an orange-red coloration and gives a somewhat redder pigment dyestufi.

A colored emulsion paint is prepared as follows: 100

' parts of a commercially available white emulsion paint (e. g. Discovin, registered trademark) are weighed out. 5 parts of a 20% aqueous paste of the above-described dyestufi are stirred into it with a brush or suitable agitator until a homogeneous mixture is obtained. The finished paint is applied to wood, paper, etc. with a brush.

EXAMPLE 5 drated by a current of dry-air. The solution, at'110--1'15,

of 20.3 parts of benzene-1.3-dicarboxylic acid chloride in 48 parts of nitrobenzene. The reaction mass is stirred for consecutive one-hour periods at 110-115", 130 and 140. The condensation product is filtered oil at 80 and washed, first with nitrobenzene at 80", then with hot alcohol and finally with hot water. furic acid with a red coloration; run into water at 50-60 in finely divided form.

100 parts of a 20% aqueous paste of the pigment dyestufi obtained according to the present example are added to 22,500 parts of an aqueous solution containing approximately 9% of viscose in a mixing vessel equipped with an agitator. The dyed viscose spinning solution is stirred for 15 minutes and is then de-aerated and subjected to the normal spinning and desulfurizing processes. The viscose rayon thus obtained is dyed in reddish violet shades.

when the solution is the pigment dyestuft is obtained EXAMPLE 6 31.7 parts of 1.4-diamino-2-bromoanthraquinone in 660 parts of 1.2-dichlorobenzene are heated to 140 and dehydrated at this temperature by means of a dry air current. To the resulting solution at 110-115 small portions of benzene-1.4-dicarboxylic acid chloride totalling 10.3 parts are added over about 2 hours and the reaction mass stirred at 130140 until such time as the starting material is no longer indicated. The condensation product thus formed is filtered oil at 80. It is washed with 1.2-dichlorobenzene at 80, then with hot alcohol and again with hot water, and finally dried.

From this product a pigment dyestulf preparation can be obtained in the manner described in Example 1. It dyes viscose spinning solutions in reddish violet shades.

EXAMPLE 7 13.6 parts of 1.4-diamino-2-chloroanthraquinone in 240 parts of nitrobenzene are heated to 140 and dehydrated by means of a dry air current. The solution, at 110", is drop-fed over a period of 2 hours with a solution of 5.1 parts of benzene-1.4-dicarboxylic acid chloride in 24 parts of nitrobenzene. The reaction mass is stirred for 2 hours at 110l15 and subsequently heated at 130 for 1 hour. Then, at 100, 100 parts of alcohol are added dropwise, whereupon the condensation product is filtered oil at 70, washed with hot alcohol and again with hot water, and dried. The pigment dyestutt obtained from it dyes viscose shades.

A linseed oil paint is prepared as follows: 20 parts of zinc white, 18 parts of boiled linseed oil and 0.2 part of the above-described dyestufi are ground together in 21 Hoover automatic miller over 400 revolutions. After every 100 revolutions the the two glass plates with a center of the rotating plate.

spatula and deposited at the When ground to the desired consistency, a suitable siccative is mixed with the paste by hand. The finished paste is applied to good-quality typewriter paper (so-called India paper) with a spatula at a thickness suflicient to cover the white ground. A red-violet linseed oil coating is obtained.

EXAMPLE 8 26.8 parts of 1.4-diamino2-methoxyanthraquinone in 660 parts of 1.2-dichlorobenzene at 140 are dehydrated with a dry air current. 13.8 parts of dimethylaminobenzene are run into the solution at 50, and a solution of 10.15 parts of benzene-1.3-dicarboxylic acid chloride in 26 parts of 1.2-dichlorobenzene is subsequently added by drop feeding over a period of 4 hours. The mass is mechanically stirred overnight at 50 and subsequently for 1 hour at 110-120.. After this time it is heated to 170 in the course of 2 hours and stirred at this temperature for 1 hour. The mass is then allowed to cool in the spinning mass in red-violet resulting paste is scraped off It dissolves in sul- EXAMPLE 9 19.6 parts of 1.4-diamino-2-(4'-methyl)-phenylsulfonylanthraquinone in 385 parts of chlorobenzene are heated to-the boil. The solution is dehydrated by distilling oil 50 parts of a chlorobenzene-water mixture, after which 5 parts of pyridine ,are added to it at 110. A solution of 5.1 parts of benzene-1.3-dicarboxylic acid chloride in 20 parts of chlorobenzene is then added dropwise in the course of 2 hours and the reaction mass stirred at 110 until the starting material is no longer indicated. Subsequently, parts of ethyl alcohol are dropped into the mass at The condensation product is filtered otf, washed with hot ethyl alcohol and then with hot water, and finally dried.

10 parts of the condensation product obtained according to the present example are re-precipitated from sulfuric acid, filtered 01f, washed and dried. The violet dyestufi powder is ground with 10 parts of secondary cellulose acetate and 160 parts of acetone in a ball mill to the requisite degree of fineness. The resulting suspension is poured into water and the product filtered ofi, washed and dried. The dyestufi obtained thus dyes cellulose acetate in the spinning mass'in bluish violet shades.

The 1.4 diamino-2-(4-methyl)-phenylsulfonylanthra quinone used as starting material was prepared by condensing an alkali metal salt of the 1.4-diaminoanthraquinone-2-sulfonic acid with 4-rnethylphenylthiol in presence of sodium or potassium hydroxide at temperatures. of between 150 and 200 and oxidizing the 1.4-diamino- 2-(4-methyl)-phenylthioanthraquinone thus obtained.

EXAMPLE 10 EXAMPLE 11 15.45 parts of 1.4-diamino-Z-bromo-6.7-dichloroanthraquinone in 300 parts of nitrobenzene at 140 are dehydrated with a dry air current. The resulting solution is drop-fed at over 2 hours witha solution of 4.0 parts of benzene-1.3-dicarboxylic acid chloride in 12 parts of nitrobenzene. The mass is stirred for 1 hour at 110, then the temperature is raised to and stirring continued until the starting material is no longer indicated. 100 parts of alcohol are added at 100; the condensation product is filtered ofi at 70, washed with hot alcohol and again with hot water, and dried. A pigment dyestufi preparation islobtained from it which dyes viscose in the spinning solution in violet shades.

EXAMPLE 12 When the 15.45 partsof 1.4-diamino-2-bromo-6.7-dichloroanthraquinone employed in Example 11 are replaced by an equivalent quantity of 1.4-diamino-2-bromo- 6-chloroanthraquinone a similar pigment dyestufi is obtained.

In the following table further N-monoacy1-1.4-diaminoanthraquinones which can be produced in accordance with one of the foregoing examples are enumerated. In the halides incolumn B.

the pigment dyestuffs when applied in viscose spinning solutions are noted.

Table Exam- A B pie No.

13-..- 1.4- Diamino-2-phloro- Adipic a'cid dichloride. bordeaux.

anthraquinone.

V v boxylicocldchloride. 15 lA Dlsmino i-bromo- Suecinic acid dichlored-violet.

anthraquinone. ride. 16 -.do Adipic acid dichloridebordeaux. 17 do Selficlc acid dichlo- D0.

18 .do 1.1 -AzobenZene-4Af-dlred-brown.

cja'rboxylie acid chlon e.

19 lA-Diamino-Z-meth- Oxalic acid dichloridereddish borowanthraqiiinone. deaux.

20 .do Fuinariodciddichlobordeaux.

21 "do Benzene-lA-dicarreddish borbcxylic acid chloride. deaux.

22 lA-Diamino-Z-ethcxy- Benzene-1.3-dicarbordeaut. anthrnquinone boxylic acid chloride.

23 1.4-Diamino-2n-prodo red-violet.

poxyantiimquinone.

24 1.4-Diamino-2pheno- .do bordeaux.

xyanthraquinone.

25 1.4 Diamlno 2 (4 Oxalic acid dichloride blue-violet.

methyl) -phenylsulfonyl anthraquizione.

Fumarlc acid dichloviolet. ride.

27 -.do Benzene-lA-dicar- Do.

boxylic acid chloride.

28 lA-Dlamino-GJ-di- .-d0 D0.

chloroanthraquinone.

29 lA-Diamino-iz-bromodo Do.

6.7 dichloro anthra quinone.

30 1.4-Diamino-2-bromo- .do D0.

o-fluoroanthrequinone.

31 lA-Diamino-zbromo- Benzene-LS-dicar- Do.

7 -chloroanthraquiboxylic acid chloride. none.

32 1.4-Diamln0-2.6-dibro- Adipic acid dichloride. reddish mocnthraquinone. violet.

33 lA Diamino-fi-fluoro- -.do D0.

anthraquinonc.

34 lA-Diomino-Z-bromo- Muconic acid dichlobordeaux.

anthraquinone. ri

35 do Malonic acid dichlo- Do.

36 Mixture of lA-diam- Benzene-1.3-diearviolet.

inc-Z-bromoanthraboxyiic acid chloride. quirione and lA-diamino=2-chloroanthraquinone.

37 Mixture of lA-diam- BenzenelA-dicarviolet to borino-2-bromoanthra- 'boxylic acid chloride. deaux. quinone and iA-diamino-2-methoxyanthraquinone.

38 .d0'. Adi'pie acid dichloride. bordeaux.

The formulae of such pigment dyestufis described in the foregoing examples are:

d NH.

EXAMPLE 1 co- HN EXAMPLE 2 In column C the shades given by 5 EXAMPLE 3 HEN EXAMPLE 4 O NH:

HzN O EXAMPLES 5 and 10 NHa NH-OC EXAMPLE 6 HIN EXAMPLE 7 NH-O COG 0-HN EXAMPLE 8 A NIH-00 10 EXAMPLE 9 O NH, H|N 0 I I O mil-Q. 6%

A NH 00 00 EN EXAMPLE 11 3. The pigment dyestufi of the anthraquinone series 0 EN 0 15 which corresponds to the formula l l Cl Br Br 01 (I) NH, EN 0 C1. Cl Br Br NH-OG CO-BN NBC-0C CO-HN EXAMPLE 12 f 4. The pigment dyestutf of the anthraquinone series which corresponds to the formula Br Br Cl 01 NH: HXN o NH-OC C0-HN B NH-OCOCO-HN EXAMPLE 16 0 m 0 40 5. The pigment dvestufi of the anthraquinone series l which corresponds to the formula.

Br Br (I? NHz HQN (I) A Cl Br Br- 01 NH-OG-CHa-CHz-CHz-CHa-CO-HN c1- 01 Having thus disclosed the lnventlon what 1s claimed 1s: 8 C CO HN 6 1. A pigment dyestufi of the anthraquinone series which corresponds to the formula 0 N H: KIN O l I 6. The pigmentdyestufi of the anthraquinone series Br r which corresponds to the formula 0 NH, Hm NEE-OC-Rz-CO-HN B wherein R stands for a member selected from the group 7 consisting of the single carbon linkage, the bivalent I methylene radical, a bivalent tetramethylene radical and O NH-O c-cm-cm-cm-om-c O-HN a bivalent phenylene radical.

2. The pigment dyestutf of the anthraquinone series which corresponds to the formula 7. A pigment dyestuif of the anthraquinone series which corresponds to the formula IFTH: HgN 0 O N H: Br B am 0 7 n I n 3 m m m NH-OO-CO-HN' 7B Nrr-0c-m-coHN 11 12 wherein each of x and x and each of y and y stands for References Gited='in-the file of this patent a member selected from the group consisting of H and Cl, UNITED STATES PATENTS and R stands for a member selected from the grou i r consisting of the single carbon linkage, the bivalent 215101088 i g 7'77" Junta 1v950: methylene radical, a bivalent tetramethylene radical and 5 2,614,109 Jenney er "f 1952 a bivalent phenylene radical. FOREIGN PATENTS 292,690 Switzerland Aug. 15, 1953 6581722 Great BritainI'I 'L III Oct. 10, 1951 857,995 Germany Oct. 9, 1952 

1. A PIGMENT DYESTUFF OF THE ANTHRAQUINONE SERIES WHICH CORRESPONDS TO THE FORMULA 